EP0443529B1 - Polysaccharide enthaltende photographische Materialien - Google Patents

Polysaccharide enthaltende photographische Materialien Download PDF

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Publication number
EP0443529B1
EP0443529B1 EP91102365A EP91102365A EP0443529B1 EP 0443529 B1 EP0443529 B1 EP 0443529B1 EP 91102365 A EP91102365 A EP 91102365A EP 91102365 A EP91102365 A EP 91102365A EP 0443529 B1 EP0443529 B1 EP 0443529B1
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EP
European Patent Office
Prior art keywords
dye
photosensitive
compounds
disclosed
dye fixing
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EP91102365A
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English (en)
French (fr)
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EP0443529A3 (en
EP0443529A2 (de
Inventor
Takeshi C/O Fuji Photo Film Co. Ltd. Shibata
Takuya C/O Fuji Photo Film Co. Ltd. Yokokawa
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Priority claimed from JP3929690A external-priority patent/JP2649853B2/ja
Priority claimed from JP10010190A external-priority patent/JPH03296736A/ja
Priority claimed from JP10310590A external-priority patent/JPH043055A/ja
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP0443529A2 publication Critical patent/EP0443529A2/de
Publication of EP0443529A3 publication Critical patent/EP0443529A3/en
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Publication of EP0443529B1 publication Critical patent/EP0443529B1/de
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/02—Photosensitive materials characterised by the image-forming section
    • G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/42—Structural details
    • G03C8/52—Bases or auxiliary layers; Substances therefor
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/136—Coating process making radiation sensitive element

Definitions

  • the invention concerns diffusion transfer photographic materials, and in particular it concerns photographic materials for diffusion transfer purposes in which various photographic characteristics have been improved.
  • the invention also concerns a method of producing a diffusion transfer photographic material.
  • the photographic technique in which silver halides are used is superior the electrophotographic and diazophotographic techniques with respect to photographic characteristics such as photographic speed and gradation control. Accordingly, in the past this has been the most widely used technique.
  • These silver halide photographic techniques include wet processing type color diffusion transfer techniques in which a dye fixing element which has a dye fixing layer is laminated with a photosensitive element which has a silver halide emulsion layer. Further, an alkaline processing composition is spread in the form of a layer within this laminate or the laminate is immersed in an alkaline processing fluid.
  • Electron donors and electron transfer agents are generally used conjointly as the reducing agent in the methods of positive image formation in which reducible dye donating compounds of the type described above are employed.
  • uneven coating is likely to arise as a result of the drying in the case of dilute aqueous solutions of the above mentioned water soluble polymers and in cases wherein a substance which inhibits gelation is added to the coating liquid.
  • unevenness in the thickness of the coated layer arises as a result of the phenomenon known as ribbing when a coating step is carried out on a support which has a certain degree of roughness.
  • natural macromolecular polysaccharides for example, natural macromolecular polysaccharides originating from red algae such as phaeceleran and carrageenans for example, and natural macromolecular polysaccharides obtained by fermentation such as "Jelan gum” for example
  • red algae such as phaeceleran and carrageenans
  • natural macromolecular polysaccharides obtained by fermentation such as "Jelan gum” for example
  • EP-A-0 247 474 discloses that the substantial compounds of a photographic record material, namely the particular silver halide emulsion and the dye donating compound, optionally in combination with an electron donor compound, may be dispersed side by side within a binder.
  • a binder thereby one can optionally use hydrophobic or hydrophilic binders, the latter being, however, preferred.
  • binders for the photosensitive layer gelatin is preferably used. It can, however, completely or partly be replaced by other natural or synthetic binders.
  • binders are suitable for example alginic acid and derivatives thereof, such as salts, esters and amides, cellulose derivatives, such as carboxy methyl cellulose, alkyl cellulose, such as hydroxy ethyl cellulose, starch and derivatives thereof, as well as carrageenates.
  • synthetic binders polyvinyl alcohol, partly saponified polyvinyl acetate and polyvinyl pyrrolidon are mentioned.
  • the objects of the present invention include diffusion transfer photographic photosensitive materials with which color images which exhibit little color transfer can be formed, diffusion transfer photographic photosensitive materials with which color photographs with little curl can be obtained, diffusion transfer photographic materials which have excellent storage stability prior to image formation, and diffusion transfer photographic photosensitive materials which provide these qualities and with which there is little drying attachment at the time of manufacture.
  • this invention is intended to provide a method of producing a diffusion transfer photographic material.
  • a diffusion transfer photographic material comprising a support having thereon at least a photosensitive element comprising a photosensitive silver halide emulsion and a diffusible dye donating compound, and a dye fixing element which is placed upon the said photosensitive element at the time of image transfer, wherein said dye fixing element contains a natural macromolecular polysaccharide originating from red algae,
  • a process of producing a diffusion transfer photographic material comprising a support having thereon at least a photosensitive element comprising a photosensitive silver halide emulsion and a diffusible dye donating compound, and a dye fixing element which is placed upon the said photosensitive element at the time of image transfer, which comprises the step of incorporating a natural macromolecular polysaccharide originating from red algae into said dye fixing element.
  • the natural polymeric polysaccharides obtained by extraction and refinement from red algae disclosed in Table 1 on page 21 of Shokuhin Kogyo , Volume 31, (1988) are among the natural macromolecular polysaccharides originating from red algae which can be used in the present invention.
  • the natural macromolecular polysaccharides obtained by extraction and refinement from red algae are mixtures of various materials. These mixtures can be used without further treatment in the present invention, or single substances of high purity can be used.
  • ⁇ -carrageenan agar, ⁇ -carrageenan, ⁇ -carrageenan, -carrageenan and phaeceleran are preferable. ⁇ -carrageenan is more preferable.
  • These substances can be procured as commercial products.
  • ⁇ -carrageenan can be obtained as "Taito Gelling Agent NK-4" which is made by the Taito Co.
  • a mixture of ⁇ -carrageenan with trace amounts of ⁇ -carrageenan can be obtained as "Taito Gelling Agent MV" which is also made by the Taito Co.
  • the amount of the natural macromolecular polysaccharide originating from red algae for the present invention can be set arbitrarily, but an amount of from 0.005 to 10 grams, and especially of from 0.02 to 4 grams, per square meter on each side of support is appropriate.
  • the natural macromolecular polysaccharides originating from red algae of the present invention may be used only in the dye fixing element, or in both the photosensitive element and the dye fixing element of a diffusion transfer photographic material.
  • the polysaccharides may be added to and used in any layer, such as a layer which contains photosensitive silver halide, a layer which contains a diffusible dye donating compound (this may be the same layer as that which contains the silver halide), a protective layer, an intermediate layer which is established between photosensitive layers of different color sensitivity, an under-layer or a backing layer. But they are preferably used in a photographic constituting layer on the same side as the photosensitive silver halide layer.
  • the polysaccharides may be in the dye fixing layer, a protective layer, an under-layer or a backing layer for example, but they are preferably used in a photographic constituting layer on the same side as the dye fixing layer.
  • the polysaccharides are especially effective for preventing color transfer when used in a dye fixing element protective layer.
  • macromolecular polysaccharides can be used conjointly with various other hydrophilic binders.
  • hydrophilic binders are preferred.
  • proteins such as gelatin and gelatin derivatives, cellulose derivatives, polysaccharides such as starch, gum arabic, dextran and pluran, poly(vinyl alcohol), polyvinylpyrrolidone, acrylamide polymers, poly(acrylic acid), poly(acrylic acid salts) and other synthetic macromolecular materials.
  • the polymers which have a high water uptake disclosed, for example, in JP-A-62-245260, which is to say homopolymers of vinyl monomers which have a -COOM group or an -SO 3 M group (where M is a hydrogen atom or an alkali metal) or copolymers of these monomers with other vinyl monomers (for example, sodium methacrylate, ammonium methacrylate, Sumikagel L-5H made by the Sumitomo Chemical Co.) can also be used. Combinations of two or more of these binders can also be used.
  • rubbers such as natural compounds (e.g., roast bean gum, tara gum and guar gum), can also be used.
  • the photosensitive elements used in the present invention are comprised fundamentally of a photosensitive silver halide emulsion and a diffusible dye donating compound on a support, and various additives such as reducing agents for example can also be used as required. These components are often added to the same layer, but if they are in a reactive state they can be added to separate layers. For example, any loss of speed is avoided if the diffusible dye donating compounds which give rise to a coloration are included in a layer below the silver halide emulsion.
  • each photosensitive layer can be divided into two or more layers, as required.
  • auxiliary layers such as protective layers, under-layers, intermediate layers, yellow filter layers, anti-halation layers, backing layers, neutralizing layers, timing layers and peeling layers for example, can also be included in the photosensitive element.
  • silver halides including silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide, can be used in the present invention.
  • the silver halide emulsions used in the present invention may be surface latent image type emulsions or internal latent image type emulsions. Internal latent image type emulsions are combined with nucleating agents or light fogging and used as direct reversal emulsions. Furthermore, so-called core/shell emulsions which have phases which have different compositions within the grain and on the grain surface layer can also be used.
  • the silver halide emulsion may be mono-disperse or poly-disperse, and mixtures of mono-disperse emulsions can be used.
  • the grain size is from 0.1 to 2 ⁇ , and most desirably from 0.2 to 1.5 ⁇ .
  • the crystal habit of the silver halide grains may be cubic, octahedral, tetradecahedral, tabular with a high aspect ratio or of some other form.
  • any of the silver halide emulsions disclosed, for example, in column 50 of U.S. Patent 4,500,626, U.S. Patent 4,628,021, Research Disclosure (referred to hereinafter as RD ) 17029 (1978), and JP-A-62-253159 can be used.
  • the silver halide emulsions can be used after ripening, but they are generally used after chemical sensitization.
  • the known methods of sulfur sensitization, reduction sensitization, precious metal sensitization and selenium sensitization, for example, can be used individually or in combinations with the emulsions for the normal type of photosensitive element.
  • These methods of chemical sensitization can also be carried out in the presence of a nitrogen containing heterocyclic compound (JP-A-62-253159).
  • those halides which have a silver bromide content of at least 50 mol ⁇ % are desirable for obtaining images which have a better S/N ratio. Furthermore, the use of those which have a silver iodide content of not more than 10 mol ⁇ % is desirable for minimizing the staining which arises after delayed development. Moreover, those halides in which the silver chloride content is 40 mol ⁇ % or less are desirable for minimizing the loss in maximum density which is produced by fogging during thermal development.
  • each photosensitive layer may consist of two or more emulsions which have different halogen compositions. Mixtures of emulsions which have different grains structures, grain forms, grain sizes, chemical sensitization, sensitizing dyes, pH, pAg, conductivity etc. are frequently used in order to achieve the intended photographic speed and gradation.
  • the emulsions used for the photosensitive element for heat-development in the present invention are preferably mono-disperse emulsions.
  • a mono-disperse emulsion is one which has a grain size distribution such that the variation coefficient (S/ r ⁇ ) for the grain size of the silver halide grains is not more than 0.25.
  • r ⁇ is the average grain size and S is the standard deviation of the grain size.
  • the performance advantage of mono-disperse emulsions is that the fogging which is produced during thermal development is minimized so that a loss of maximum density is less likely to arise.
  • This fogging is especially pronounced as a feature of thermal development when compared to conventional photosensitive materials (color papers, color negatives etc.) with which liquid development is generally used.
  • the optimum point of chemical sensitization for an emulsion has long been known to be greatly dependent on the grain size.
  • more grains can be chemically sensitized close to the optimum level in cases where a mono-disperse emulsion is being used.
  • the small size grains are not chemically sensitized adequately and the photographic speed is reduced, while the large sized grains are chemically sensitized to excess. This results in a high fog level and, overall, the performance is that of soft contrast, low speed and a high fog level.
  • chemical sensitization is important for providing photosensitive elements of high photographic speed of course and this is generally the same as for a conventional sensitive material.
  • the inventors have reported before that with gold/sulfur sensitization, fogging is especially likely to occur and that the optimum amount of gold is from 1 x 10 -7 to 1.0 x 10 -5 per mol of silver (JP-A-1-233440).
  • the present invention can be recognized as being especially effective in mono-disperse emulsions which have been gold/sulfur sensitized.
  • the coated weight of photosensitive silver halide used in the present invention is within the range from 1 mg to 10 grams per square meter calculated as silver.
  • the silver halide used in this invention may be spectrally sensitized with methine dyes or by other means.
  • the dyes which may be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemi-cyanine dyes, styryl dyes and hemi-oxonol dyes.
  • Examples include the sensitizing dyes disclosed, for example, in U.S. Patent 4,617,257, JP-A-59-180550, JP-A-60-140335 and RD 17029 (1978) pages 12 - 13.
  • sensitizing dyes can be used individually, or combinations of these dyes can be used. Combinations of sensitizing dyes are often used especially with the aim of achieving super-sensitization.
  • Compounds which exhibit super-sensitization which is to say dyes which themselves have no spectrally sensitizing action or compounds which essentially do not absorb visible light (for example, those disclosed in U.S. Patent 3,615,641 and JP-A-63-23145), may be included together with the sensitizing dyes.
  • sensitizing dyes may be adsorbed to the emulsion during, before or after chemical sensitization, and they may be added before or after nuclei formation for the silver halide grains as disclosed in U.S. Patents 4,183,756 and 4,225,666.
  • the amount adsorbed is generally from 10 -8 to 10 -2 mol per mol of silver halide.
  • Methods of using various sensitizing dyes can be applied to heat developable photosensitive elements of the present invention as described above, but those methods in which sensitizing dyes are added prior to chemical sensitization are preferred. This is because emulsions to which sensitizing dyes have been added prior to chemical sensitization exhibit less fogging at high photographic speeds than comparative emulsions and because the fog reducing effect of the natural macromolecular polysaccharides originating from red algae of the present invention is more pronounced under these conditions.
  • the diffusible dye donating compounds used in the present invention are compounds which generate or release diffusible dyes in accordance with the reaction or in counter-accordance with the reaction when a silver ion is reduced to silver. These compounds are all referred to hereinafter as dye donating compounds for the sake of simplicity.
  • Examples of dye donating compounds which can be used in the present invention include first of all the compounds (couplers) which form dyes by means of an oxidative coupling reaction. These couplers may be four-equivalent couplers or two-equivalent couplers, but two-equivalent couplers which have a non-diffusible group as a leaving group and form a diffusible dye by means of an oxidative coupling reaction are preferred.
  • the non-diffusible group may take the form of a polymer chain. Examples of color developing agents and couplers have been described in detail in, for example, The Theory of the Photographic Process , by T.H.
  • JP-A-58-123533 JP-A-58-149046, JP-A-58-149047, JP-A-59-111148, JP-A-59-124399, JP-A-59-174835, JP-A-59-231539, JP-A-59-231540, JP-A-60-2950, JP-A-60-2951, JP-A-60-14242, JP-A-60-23474 and JP-A-60-66249.
  • compounds which have the function of releasing or dispersing dispersible dyes in the form of the image are another type of dye donating compound.
  • Compounds of this type can be represented by the general formula (LI) indicated below: (Dye-Y) n -Z
  • Dye represents a dye group, a dye group which has been temporarily shifted to the short wave length side or a dye precursor group
  • Y represents a single bond or a linking group
  • Z represents a group which produces a difference in the diffusibility of the compound represented by (Dye-Y) n -Z or which releases Dye and produces a difference in the diffusibilities of the released Dye and(Dye-Y) n -Z , in accordance or in counter-accordance with the photosensitive silver salt in which a latent image has been formed in the form of the image
  • n represents 1 or 2, and when n is 2 the two Dye-Y moieties may be the same or different.
  • Examples of dye donating compounds represented by general formula (LI) include the compounds described under the headings (1) to (5) below. Moreover, the compounds described under the headings (1) to (3) below form diffusible dye images in counter-accordance with the development of the silver halide (positive dye images) and those described under the headings (4) and (5) form diffusible dye images in accordance with the development of the silver halide (negative dye images):
  • Examples include: compounds which release diffusible dyes by means of an intramolecular nucleophilic substitution reaction after reduction disclosed, for example, in U.S. Patents 4,139,389 and 4,139,379, JP-A-59-185333 and JP-A-57-84453; compounds which release a diffusible dye by means of an intramolecular electron transfer reaction after reduction disclosed, for example, in U.S. Patent 4,232,107, JP-A-59-101649, JP-A-61-88257 and RD 24025 (1984); compounds which release a diffusible dye via single bond cleavage after reduction disclosed, for example, in West German Patent 3,008,588A, JP-A-56-142530, and U.S.
  • Patents 4,343,893 and 4,619,884 the nitro compounds which release diffusible dyes after accepting an electron disclosed, for example, in U.S. Patent 4,450,223 and the compounds which release diffusible dyes after accepting an electron disclosed, for example, in U.S. Patent 4,609,610.
  • Patent 4,783,396, JP-A-63-201653 and JP-A-63-201654 compounds which have electron withdrawing groups and an SO 2 -X bond (where X has the same significance as described above) within the molecule disclosed in JP-A-1-26842, compounds which have electron withdrawing groups and a PO-X bond (where X has the same significance as described above) within the molecule as disclosed in JP-A-63-271344, and compounds which have electron withdrawing groups and a C-X' bond (where X' is the same as X or -SO 2 -) disclosed in JP-A-63-271341.
  • Examples include compounds (11) - (23) disclosed in Kokai Giho 87-6199, and compounds (1) - (3), (7) - (10), (12), (13), (15), (23) - (26), (31), (32), (35), (36), (40), (41), (44), (53)- (59), (64) and (70) disclosed in U.S. Patent 4,783,396 and in European Patent 220,746A2.
  • the dye-silver compounds in which a dye is bonded to an organic silver salt ( Research Disclosure May 1978, pages 54 - 58 for example), the azo dyes which are used in the heat-developable silver dye bleach method (U.S. Patent 4,235,957, Research Disclosure , April 1976, pages 30 - 32 for example), and leuco dyes (U.S. Patents 3,985,565 and 4,022,617 for example) can also be used as dye donating compounds other than the couplers and compounds of general formula (LI) described above.
  • anti-fogging agents or photographic stabilizers can be used in the present invention.
  • use can be made of the azoles and azaindenes disclosed on pages 24 - 25 of RD 17643 (1978), the nitrogen containing carboxylic acids and phosphoric acids disclosed in JP-A-59-168442 or the mercapto compounds and their metal salts as disclosed in JP-A-59-111636 and the acetylene compounds disclosed in JP-A-62-87957.
  • hydrophilic binders for the binder in the constituting layers of the photosensitive elements and dye fixing elements other than the layer which contains the aforementioned natural macromolecular polysaccharide originating from red algae is desirable.
  • examples include those disclosed on pages 26 - 28 of JP-A-62-253159.
  • transparent or semi-transparent hydrophilic binders are preferred.
  • proteins such as gelatin and gelatin derivatives, and other natural compounds such cellulose derivatives and polysaccharides such as starch, gum arabic, dextran and pluran, and poly(vinyl alcohol), polyvinylpyrrolidone, acrylamide polymers and other synthetic polymeric compounds.
  • JP-A-62-245260 which is to say homopolymers of vinyl monomers which have a -COOM group or an -SO 3 M group (where M represents a hydrogen atom or an alkali metal) or copolymers of these vinyl monomers, or copolymers of these vinyl monomers with other vinyl monomers (for example, sodium methacrylate, ammonium methacrylate, Sumikagel L-5H made by the Sumitomo Chemical Co.), can also be used. Two or more of these binders can also be used in combination.
  • the coated weight of the binder in the present invention is preferably not more than 20 grams per square meter, and more desirably it is not more than 10 grams per square meter, while most desirably it is not more than 7 grams per square meter.
  • Various polymer latexes can be included in a constituting layer (including the backing layers) of the photosensitive element or dye fixing element with a view to improving film properties such as providing dimensional stabilization, preventing the occurrence of curl, preventing the occurrence of sticking, preventing the formation of cracks in the film and preventing the occurrence of pressure desensitization.
  • film properties such as providing dimensional stabilization, preventing the occurrence of curl, preventing the occurrence of sticking, preventing the formation of cracks in the film and preventing the occurrence of pressure desensitization.
  • Examples include all of the polymer latexes disclosed, for example, in JP-A-62-245258, JP-A-62-136648 and JP-A-62-110066.
  • organometallic salts can be used conjointly as oxidizing agents along with the photosensitive silver halide.
  • the use of organic silver salts from among these organometallic salts is especially desirable.
  • the benzotriazoles, fatty acids and other compounds disclosed, for example, in columns 52 - 53 of U.S. Patent 4,500,626 can be used as organic compounds for forming the organic silver salt oxidizing agents mentioned above.
  • the silver salts of carboxylic acids which have alkynyl groups such as the silver phenylpropiolate disclosed in JP-A-60-113235, and the silver acetylenes disclosed in JP-A-61-249044, can also be used. Two or more organic silver salts can be used conjointly.
  • organic silver salts can be used conjointly in amounts of from 0.01 to 10 mol, and preferably of from 0.01 to 1 mol, per mol of photosensitive silver halide.
  • the total amount of photosensitive silver halide and organic silver salt coated is suitably from 50 mg to 10 grams per square meter when calculated as silver.
  • the reducing agent may be incorporated into the photosensitive element or it may be supplied to the photosensitive element (and the dye fixing element) at the time of processing as one component of a processing composition which is contained in a burstable container.
  • the former embodiment is preferred when processing is carried out with thermal development and the latter embodiment is preferred when processing is carried out at a near normal temperature using a so-called color diffusion transfer process.
  • any of the reducing agents known in this field can be used.
  • the dye donating compounds which have reducing properties described hereinafter can also be included (other reducing agents can also be used conjointly in this case).
  • reducing agent precursors which themselves have no reducing properties but which achieve reducing properties as a result of the action of a nucleophilic reagent or heat during the development process can also be used.
  • Patents 4,330,617 and 4,590,152 pages 17 - 18 of JP-A-60-140335, JP-A-57-40245, JP-A-56-138736, JP-A-59-178458, JP-A-59-53831, JP-A-59-182449, JP-A-59-182450, JP-A-60-119555, JP-A-60-128436 to JP-A-60-128439, JP-A-60-198540, JP-A-60-181742, JP-A-61-259253, JP-A-62-244044, JP-A-62-131253 to JP-A-62-131256, and pages 78 - 96 of European Patent 220,746A2.
  • combinations with an electron transfer agent and/or an electron transfer agent precursor can be used in order to promote electron transfer between the non-diffusible reducing agent and the developable silver halide.
  • Electron transfer agents or precursors thereof can be selected from among the reducing agents and precursors thereof described earlier.
  • the electron transfer agent or precursor thereof preferably has a higher degree of diffusibility than the non-diffusible reducing agent (electron donor).
  • 1-Phenyl-3-pyrazolidones and aminophenols are especially useful electron transfer agents.
  • the reducing agents (electron donors) which are non-diffusible which are used in combination with the electron transfer agents should be those from among the aforementioned reducing agents which are essentially immobile in the layers of the photosensitive element.
  • Preferred examples include hydroquinones, sulfonamidophenols, sulfonamidonaphthols, the compounds disclosed as electron donors in JP-A-53-110827 and the dye donating compounds which have reducing properties but which are non-diffusible as described hereinafter.
  • the amount of reducing agent added is generally from 0.001 to 20 mol, and more desirably from 0.01 to 10 mol, per mol of silver.
  • hydrophobic additives such as the dye donating compounds and non-diffusible reducing agents for example can be introduced into the layers of the photosensitive element using known methods such as those described, for example, in U.S. Patent 2,322,027.
  • high boiling point organic solvents such as those disclosed, for example in JP-A-59-83154, JP-A-59-178451, JP-A-59-178452, JP-A-59-178453, JP-A-178454, JP-A-59-178455 and JP-A-59-178457 can be used conjointly with low boiling point organic solvents of a boiling point from 50°C to 160°C, as required.
  • the amount of high boiling point organic solvent is generally not more than 10 grams, and preferably not more than 5 grams, per gram of dye donating compound used. Furthermore, they are suitably used in amounts of not more than 1 cc, preferably not more than 0.5 cc, and most desirably not more than 0.3 cc, per gram of binder.
  • the compounds can be included by dispersion as fine particles in the binder as well as using the method described above.
  • Various surfactants can be used when hydrophobic compounds are being dispersed in a hydrophilic colloid. For example, use can be made of the surfactants disclosed on pages 37 - 38 of JP-A-59-157636.
  • a dye fixing element is used along with the photosensitive element.
  • the dye fixing element may be coated separately on a separate support from the photosensitive element or it may be coated on the same support as the photosensitive element.
  • the relationships disclosed in column 57 of U.S. Patent 4,500,626 can also be used here as the relationship between the photosensitive element and the dye fixing element and the relationship with the support and the relationship with a white reflecting layer.
  • the dye fixing elements preferably used in the present invention have at least one layer which contains a mordant and a binder.
  • the mordants known in the field of photography can be used, and examples include the mordants disclosed in columns 58 - 59 of U.S. Patent 4,500,626 and on pages 32 - 41 of JP-A-61-88256, and those disclosed in JP-A-62-244043 and JP-A-62-244036.
  • transition metal ions may be included for chelation by the dyes which have diffused.
  • Other methods of fixing dyes include the use of polymeric compounds which have dye accepting properties such as those disclosed in U.S. Patent 4,463,079.
  • Auxiliary layers such as protective layers, peeling layers, neutralizing layers, timing layers and anti-curl layers, can be established, as required, in a dye fixing element.
  • the establishment of a protective layer is especially useful.
  • High boiling point organic solvents can be used as plasticizers, slip agents or as agents for improving the peeling properties of the photosensitive element and the dye fixing element in the constituting layers of the photosensitive and dye fixing elements.
  • plasticizers can be used as plasticizers, slip agents or as agents for improving the peeling properties of the photosensitive element and the dye fixing element in the constituting layers of the photosensitive and dye fixing elements.
  • use can be made of those disclosed, for example, on page 25 of JP-A-62-253159 and JP-A-62-245253.
  • various silicone oils can be used for the above mentioned purpose.
  • the various modified silicone oils described in data sheet P6-18B, "modified Silicone Oils”, put out by the Shinetsu Silicone Co., and especially the carboxy modified silicone (trade name X-22-3710) are effective.
  • silicone oils disclosed in JP-A-62-215953 and JP-A-63-46449 are also effective.
  • Anti-color fading agents may be used in the photosensitive elements and dye fixing elements. Antioxidants, ultraviolet absorbers and certain types of metal complex can be used as anti-color fading agents.
  • antioxidants examples include chroman based compounds, coumaran based compounds, phenol based compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane based compounds. Furthermore, the compounds disclosed in JP-A-61-159644 are also effective.
  • Anti-color fading agents for preventing the fading of dyes which have been transferred to the dye fixing element may be included beforehand in the dye fixing element or they may be supplied to the dye fixing element from the outside, for instance from the photosensitive element.
  • antioxidants ultraviolet absorbers and metal complexes may be used in combinations of each type.
  • Fluorescent whiteners may be used in the photosensitive and dye fixing elements.
  • fluorescent whiteners are preferably incorporated into the dye fixing element or supplied to the dye fixing element from the outside, or from the photosensitive element, for example.
  • the compounds disclosed, for example, in chapter 8 of volume V of The Chemistry of Synthetic Dyes, by K. Veenkataraman, and JP-A-61-143752 can be used.
  • use can be made, for example, of stilbene based compounds, coumarin based compounds, biphenyl based compounds, benzoxazole based compounds, naphthalimide based compounds, pyrazoline based compounds and carbostiryl based compounds.
  • Fluorescent whiteners can be used in combination with anti-color fading agents.
  • the film hardening agents disclosed, for example, in column 41 of U.S. Patent 4,678,739, JP-A-59-116655, JP-A-62-245261 and JP-A-61-18942 can be used as film hardening agents in the constituting layers of the photosensitive and dye fixing elements.
  • aldehyde based film hardening agents (formaldehyde for example), aziridine based film hardening agents, epoxy based film hardening agents for example), vinylsulfone based film hardening agents (N,N'-ethylene-bis(vinylsulfonylacetamido)ethane) for example), N-methylol based film hardening agents (dimethylol urea for example), and polymeric film hardening agents (the compounds disclosed, for example, in JP-A-62-234157).
  • surfactants can be used in the constituting layers of the photosensitive and dye fixing elements as coating aids, for improving peelability, for improving slip properties, for anti-static purposes or for accelerating development for example.
  • examples of surfactants have been disclosed, for example, in JP-A-62-173463 and JP-A-62-183457.
  • Organic fluorine compounds may be included in the constituting layers of the photosensitive and dye fixing elements with a view to improving slip properties, for anti-static purposes or for improving peeling properties, for example.
  • Typical examples of organic fluorine compounds include the fluorine based surfactants disclosed, for example, in columns 8 - 17 of JP-B-57-9053, JP-A-61-20944 and JP-A-62-135826, and the oil-like fluorine based compounds such as fluorine oil and hydrophobic fluorine compounds including solid fluorine compound resins such as ethylenetetrafluoride resins.
  • Matting agents can be used in the photosensitive and dye fixing elements. Additionally, the silicon dioxide and polyolefin or polymethacrylate disclosed on page 29 of JP-A-61-88256, the compounds disclosed in JP-A-63-274944 and JP-A-63-274952, such as benzoguanamine resin beads, polycarbonate resin beads and AS resin beads, for example, can be used as matting agents.
  • thermal solvents may be included in the photosensitive and dye fixing elements.
  • anti-foaming agents may be included in the photosensitive and dye fixing elements.
  • colloidal silica may be included in the photosensitive and dye fixing elements. Examples of these additives have been disclosed on pages 26 - 32 of JP-A-61-88256.
  • Image forming accelerators can be used in the photosensitive elements and/or dye fixing elements.
  • the use of image forming accelerators is especially desirable in cases where processing is carried out using thermal development.
  • Image forming accelerators are compounds which accelerate the redox reaction of the silver salt oxidizing agents and the reducing agent, accelerate the reaction which produces the dye from the dye donating substance, which breaks down the dye or which releases a diffusible dye, and accelerate the migration of the dye to the dye fixing layer.
  • these accelerators can be divided into bases or base precursors, nucleophilic compounds, high boiling point organic solvent (oils), thermal solvents, surfactants, and compounds which interact with silver or silver ion, for example.
  • these groups of substances generally have a complex function and normally combine some of the above mentioned accelerating effects. Details have been disclosed in columns 38 - 40 of U.S. Patent 4,678,739.
  • Base precursors are, for example, salts of a base and an organic acid which is decarboxylated by heating, or compounds which release amines by an intramolecular nucleophilic substitution reaction, a Lossen rearrangement or a Beckmann rearrangement. Examples have been disclosed, for example, in U.S. Patent 4,511,493 and JP-A-62-65038.
  • the base or base precursor is preferably included in the dye fixing element to ensure good storage properties for the photosensitive element.
  • the combinations of sparingly soluble metal compounds and compounds which can take part in a complex forming reaction (known as complex forming compounds) with the metal ions from which these sparingly soluble metal compounds are formed disclosed in European Patent Laid Open 210,660 and U.S. Patent 4,740,445, and the compounds which produce bases by electrolysis disclosed in JP-A-61-232451, for example, can also be used as base precursors.
  • the former method is particularly effective.
  • the sparingly soluble metal compound and the complex forming compound are usefully added separately to the photosensitive element and the dye fixing element.
  • Various development terminating agents can be used in the photosensitive elements and/or dye fixing elements of the present invention with a view to obtaining a constant image irrespective of fluctuations in the processing temperature and the processing time during development.
  • development terminator signifies a compound which, after proper development, neutralizes the base or reacts with the base, reduces the base concentration in the film and terminates development, or a compound which interacts with silver and silver salts and thereby inhibits development.
  • these compounds include acid precursors which release an acid on heating, electrophilic compounds which undergo substitution reactions with a base on heating, and nitrogen containing heterocyclic compounds, mercapto compounds and precursors of these compounds. Further details have been disclosed on pages 31 - 32 of JP-A-62-253159.
  • Paper and synthetic polymers are generally used for the support of the photosensitive elements and dye fixing elements used in the present invention.
  • supports comprised of poly(ethylene terephthalate), polycarbonate, poly(vinyl chloride), polystyrene, polypropylene, polyimide, cellulose derivatives (for example, triacetylcellulose) or supports wherein a pigment such as titanium oxide is included within these films, film type synthetic papers made from polypropylene, papers made from a synthetic resin, such as polyethylene, pulp and natural pulp, Yankee paper, baryta paper, coated papers (especially cast coated papers), metals, cloths and glasses for example.
  • These supports can be used individually, or supports which have been laminated on one side or on both sides with a synthetic polymer such as polyethylene for example can also be used.
  • Hydrophilic binder and a semiconductive metal oxide such as tin oxide or alumina sol, carbon black and other anti-static agents may be coated on the surface of the support.
  • the methods which can be used for exposing and recording an image on a photosensitive element include: (1) those in which the picture of a view or a person is taken directly using a camera for example, (2) methods in which an exposure is made though a reversal film or a negative film using a printer or an enlarger, (3) methods in which a scanning exposure of an original is made through a slit using the exposing device of a copying machine for example, (4) methods in which the exposure is made with light emitted from a light emitting diode or various types of laser, being controlled by an electrical signal in accordance with picture information, and (5) methods in which exposures are made directly or via an optical system using the output of an image display device such as a CRT, a liquid crystal display, an electro-luminescent display or a plasma display.
  • an image display device such as a CRT, a liquid crystal display, an electro-luminescent display or a plasma display.
  • image exposures can also be made using wave-length conversion elements in which a non-linear optical material is combined with a coherent light source such as laser light.
  • a non-linear optical material is a material which when irradiated with a strong photoelectric field such as laser light, exhibits a non-linearity between the apparent polarization and the electric field.
  • Inorganic compounds typified by lithium niobate, potassium dihydrogen phosphate (KDP), lithium iodate and BaB 2 O 4 , and urea derivatives, nitroaniline derivatives, nitropyridine-N-oxide derivatives such as 3-methyl-4-nitropyridine-N-oxide (POM) for example, and the compounds disclosed in JP-A-61-53462 and JP-A-62-210432 are preferably used for this purpose.
  • KDP potassium dihydrogen phosphate
  • Liodate lithium iodate
  • BaB 2 O 4 urea derivatives
  • nitroaniline derivatives nitropyridine-N-oxide derivatives
  • POM 3-methyl-4-nitropyridine-N-oxide
  • Any of the known embodiments of wavelength converting elements such as the single crystal optical wave guide type and the fibre type can be used.
  • the aforementioned image information may be an image signal which has been obtained using a video camera or an electronic still camera for example, a television signal as typified by the Japanese television signal specification (NTSC), an image signal obtained by dividing an original into a plurality of picture elements using a scanner for example, or an image signal which has been generated using a computer as typified by CG and CAD.
  • NTSC Japanese television signal specification
  • CG and CAD computer as typified by CG and CAD
  • the photosensitive element and/or dye fixing element may be such that they have an electrically conductive heat generating layer as a means of heating for thermal development purposes or for the diffusion transfer of dyes by heating.
  • an electrically conductive heat generating layer as disclosed in JP-A-61-145544 can be used.
  • such an electrically conductive layer also functions as an anti-static layer.
  • Diffusion transfer photographic materials of the present invention may be processed using the so-called color diffusion transfer method in which image formation is achieved using an alkali processing composition at close to normal temperature, or they may be processed by thermal development.
  • the various known systems can be adopted for the color diffusion transfer method.
  • Thermal development is possible at temperatures of from about 50°C to about 250°C, but heating temperatures of from about 80°C to about 180°C are especially useful in the thermal development process.
  • a dye diffusion transfer process may be carried out at the same time as thermal development, or it may be carried out after the completion of the thermal development process. In the latter case, transfer is possible with heating temperatures for the transfer process within the range from the temperature in the thermal development process to room temperature, but temperatures of at least 50°C but about 10°C lower than the temperature during the thermal development process are preferred.
  • Dye transfer can be achieved by heat alone, but solvents may be used in order to promote dye migration.
  • the methods in which development and transfer are carried out simultaneously or continuously by heating in the presence of a small amount of solvent (especially water) as described in detail in JP-A-59-218443 and JP-A-61-238056 are also useful.
  • the heating temperature is preferably at least 50°C but the boiling point of the solvent or less and, for example, when water is used as the solvent a temperature of at least 50°C but 100°C or less is desirable.
  • Water or a basic aqueous solution which contains an inorganic alkali metal salt or an organic salt are examples of solvents which can be used to accelerate development and/or to transfer a diffusible dye into the dye fixing layer.
  • solvents which can be used to accelerate development and/or to transfer a diffusible dye into the dye fixing layer.
  • low boiling point solvents or mixtures of low boiling point solvents and water or basic aqueous solutions can also be used.
  • surfactants, anti-fogging agents, and sparingly soluble metal salts and complex forming compounds may be included in the solvent.
  • solvents may be applied to the dye fixing element, to the photosensitive element or to both of these elements.
  • the amount used should be small, being less than the amount of solvent corresponding to the maximum swelled volume of the whole coated film (in particular, less than the amount obtained on subtracting the weight of the whole coated film from the weight of the solvent corresponding to the maximum swelled volume of the whole coated film).
  • the method described on page 26 of JP-A-61-147244 can be used, for example, for applying the solvent to the photosensitive layer or dye fixing layer.
  • the solvent can also be incorporated into the photosensitive element, the dye fixing element or both of these elements beforehand in a form in which it has been enclosed by micro-encapsulation.
  • hydrophilic thermal solvent which is a solid at normal temperature but which melts at elevated temperatures is incorporated in the photosensitive element or dye fixing element
  • the hydrophilic thermal solvent may be incorporated into the photosensitive element or the dye fixing element, or it may be incorporated into both of these elements.
  • the layer into which it is incorporated may be an emulsion layer, an intermediate layer, a protective layer or a dye fixing layer, but it is preferably incorporated into a dye fixing layer and/or a layer adjacent thereto.
  • hydrophilic thermal solvents examples include ureas, pyridines, amides, sulfonamides, imides, alnyles (sic), oximes and other heterocyclic compounds.
  • high boiling point organic solvents may be included in the photosensitive element and/or dye fixing element in order to accelerate dye migration.
  • the material is brought into contact with a heated block or plate, sometimes the material is brought into contact with a hot plate, a hot presser, a heated roller, a halogen lamp heater or an infrared or far-infrared lamp heater for example, and sometimes the material is passed through a high temperature atmosphere as a means of heating in the development and/or transfer process.
  • thermo development devices can be used for processing the photographic elements of the present invention.
  • use of the devices disclosed, for example, in JP-A-59-75247, JP-A-59-177547, JP-A-59-181353, JP-A-60-18951 and JP-A-U-62-25944 is desirable.
  • JP-A-U as used herein signifies an "unexamined published Japanese utility model application”.
  • the problems are resolved by a method of coating hydrophilic polymers wherein a coating liquid which contains a solution of a water soluble polymer which has been obtained by adding water after dispersing the aforementioned water soluble polymer in the aforementioned hydrophilic organic solvent and forming a solution or by dissolving the aforementioned water soluble polymer in a mixed solution of the aforementioned hydrophilic organic solvent and water is used.
  • a natural macromolecular substance such as gelatin for example can be used for the water soluble polymer which undergoes a reversible sol/gel transformation on heating and cooling an aqueous solution which is used in the present invention.
  • gelatins such as acid treated gelatin, lime treated gelatin and enzyme treated gelatin for example, can be used for the gelatin, and the gelatin may be a hide gelatin or a bone (ossein) gelatin.
  • the gelatin may be a hide gelatin or a bone (ossein) gelatin.
  • lime treated ossein gelatin is used.
  • Lime treated ossein gelatin which has been subjected to a calcium removal process can also be used.
  • the dye fixing element contains a natural macromolecular polysaccharide originating from red algae.
  • the natural macromolecular polysaccharides obtained by extraction and refinement from red algae disclosed in table 1 on page 21 of Shokuhin Kogyo , Volume 31 (1988) can be cited as natural macromolecular polysaccharides.
  • the natural macromolecular polysaccharide originating from red algae is comprised of a mixture of various polysaccharides. In the present invention, these mixtures may be used as they are, or single highly purified material can be used.
  • ⁇ -carrageenan can be obtained as Taito Gelling Agent NK-4 made by the Taito Co.
  • a material comprising of trace amount of ⁇ -carrageenan in ⁇ -carrageenan can be obtained as Taito Gelling Agent MV, also made by the Taito Co.
  • the water soluble polymer as described above is preferably transformed into a solution by adding water after dispersing the said water soluble polymer in a hydrophilic organic solvent in which the polymer is essentially insoluble to make a solution or by dissolving the aforementioned water soluble polymer in a mixed solution of the aforementioned hydrophilic organic solvent and water (this is referred to as a solution of a water soluble polymer of the present invention).
  • This solution is used as a direct coating liquid or it is mixed with an aqueous solution of another water soluble polymer which has a binder forming action, and then used as a coating liquid. It is possible in this way to dissolve the water soluble polymer rapidly without forming undissolved lumps which are known as "butsu", "dama” and "mamako" for example.
  • the hydrophilic organic solvents which can be used for preparing the solution of a water soluble polymer used in the present invention are organic solvents in which the above mentioned water soluble polymers are essentially insoluble and which can be mixed without separation with water in a form in which the water contains at least 30 wt.% of the organic solvent. Those solvents which can be removed by evaporation from the coated film in the post-coating drying process are especially desirable. Thus, organic solvents whose boiling point is 100°C or less are preferred.
  • hydrophilic organic solvents include alcohols (for example, methanol, ethanol, propanol, butanol), ketones (for example, acetone, methyl ethyl ketone) and mixtures of these solvents, but methanol, ethanol and methyl ethyl ketone are especially desirable.
  • each component used in the preparation of a solution of a water soluble polymer used in the present invention are arbitrary, but the use of generally from 0.1 to 20 parts by weight, and more desirably of from 1 to 10 parts by weight, of hydrophilic organic solvent per 1 part by weight of water soluble polymer used in the present invention and of at least 10 parts by weight, and most desirably of from 10 to 100 parts by weight, of water per 1 part by weight of water soluble polymer used in the present invention is preferred.
  • the solution of water soluble polymer used in the present invention is taken as it is or after being mixed with a solution of another water soluble polymer which has a binder forming action (for example, an aqueous gelatin solution which has been prepared in a separate procedure) as a coating liquid and this is coated on an appropriate support.
  • a solution of another water soluble polymer which has a binder forming action for example, an aqueous gelatin solution which has been prepared in a separate procedure
  • the method of coating used in the present invention can be applied to materials for various applications in which a water soluble polymer is used as a binder.
  • examples include ink jet recording papers, heat sensitive papers, heat sensitive copy papers, analytical elements for medical diagnostic purposes, plotter papers, auto-radiographic developing elements, optical filters, silver halide photosensitive materials and image receiving materials.
  • Silver halide photosensitive materials are materials which contain silver halides as photosensitive materials.
  • the coating method used in the present invention can be used for coating photosensitive layers and other constituting layers (for example, over-coating layers, intermediate layers, underlayers, anti-halation layers, filter layers, backing layers, anti-static layers, diffusible dye donating layers, water absorbing layers, processing agent supplying layers, electrical heat generating layers) of these photosensitive materials.
  • the method of coating used in the present invention can be used for coating image receiving layers and other constituting layers (for example, over-coating layers, intermediate layers, under-layers, backing layers, electrical heat generating layers, water absorbing layers, white reflecting layers, neutralizing layers and timing layers) of image receiving materials.
  • image receiving layers and other constituting layers for example, over-coating layers, intermediate layers, under-layers, backing layers, electrical heat generating layers, water absorbing layers, white reflecting layers, neutralizing layers and timing layers
  • any of the silver halides silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used in the photographic emulsion layers of a photographic photosensitive material to which the present invention is applied.
  • the silver halide grains in the photographic emulsion may be so-called regular grains which have a regular crystalline form such as a cubic, octahedral or tetradecahedral form, or they may have an irregular crystalline form such as a spherical form, or they may have crystal defects such as twinned crystal planes for example, or they may have a form which is a composite of these forms.
  • the size of the silver halide grains may be very small at less than about 0.1 microns, or the grains may be of a large size with a projected area diameter of up to about 10 microns.
  • the emulsions may be mono-disperse emulsions with a narrow grain size distribution or poly-disperse emulsions with a wide grain size distribution.
  • the photographic emulsions used in the invention can be prepared using the methods described by P. Glafkides in Chimie et Physique Photographique , published by Paul Montel, 1967, by G. F. Duffin in Photographic Emulsion Chemistry , published by Focal Press, 1966, and by V. L. Zelikmann et al. in Making and Coating Photographic Emulsions , published by Focal Press, 1964. That is to say, acidic methods, neutral methods or ammonia methods can be used. A single sided mixing method, a simultaneous mixing method, or a combination of these methods may be used for the system by which the soluble halogen salt is reacted with the soluble silver salt.
  • Mixtures of two or more types of silver halide emulsion which have been prepared separately may be used.
  • Silver halide emulsions comprised of the aforementioned regular grains can be obtained by adjusting the pAg and pH values during grain formation. Details have been disclosed, for example, on pages 159 - 165 of Photographic Science and Engineering , Vol. 6, 1962, on pages 242 - 251 of Journal of Photographic Science , Vol. 12, 1964, and in U.S. Patent 3,655,394 and British Patent 1,413,748.
  • Mono-disperse emulsions have been disclosed, for example, in JP-A-48-8600, JP-A-51-39027, JP-A-51-83097, JP-A-53-137133, JP-A-54-48521, JP-A-54-99419, JP-A-58-37635, JP-A-58-49938, JP-B-47-11386, U.S. Patent 3,655,394 and British Patent 1,413,748.
  • tabular grains of which the aspect ratio is at least 5 can also be used in this invention.
  • Tabular grains can be prepared easily using the methods described, for example, by Cleve in Photography Theory and Practice page 131, (1930), by Gutoff in Photographic Science and Engineering , Vol. 14, pages 248 - 257 (1970), and in U.S. Patents 4,434,226, 4,414,310, 4,433,048 and 4,439,520, and in British Patent 2,112,157.
  • the covering power is increased and in that the color sensitization efficiency with sensitizing dyes is increased. Details have been given in the previously cited U.S. Patent 4,434,226.
  • the crystal structure may be uniform, or it may take a form comprising inner and outer parts which have different halogen compositions and a layer structure may be formed.
  • emulsion grains have been disclosed, for example, in British Patent 1,027,146, U.S. Patents 3,505,068 and 4,444,877, and in JP-A-60-143331.
  • silver halides which have different compositions may be joined epitaxially, or they may be joined with compounds other than silver halides, such as silver thiocyanate or lead oxide.
  • Such emulsion grains have been disclosed, for example, in U.S. Patents 4,094,684, 4,142,900 and 4,459,353, British Patent 2,038,792, U.S. Patents 4,349,622, 4,395,478, 4,433,501, 4,463,087, 3,656,962 and 3,852,067, and JP-A-59-162540.
  • Mixtures of grains of various crystalline forms may be used.
  • Silver halide solvents are useful for accelerating ripening. For example, it is known that ripening is accelerated with the presence of excess halogen ion in the reactor. Consequently, it is clear that ripening can be accelerated simply by introducing a solution of halide into the reactor.
  • Other ripening agents can be used, and these ripening agents can be combined in total with the dispersion medium in the reactor prior to the addition of the silver and halide or they can be introduced into the reactor together with the addition of one or two or more than two of the halides, silver salts and deflocculating agents. In another embodiment, the ripening agents are introduced independently at the halide or silver salt addition stage.
  • Ammonia or amine compounds, and thiocyanates for example alkali metal thiocyanates and ammonium thiocyanate, can be used as ripening agents as well as halogen ions.
  • thiocyanate ripening agents has been described in U.S. Patents 2,222,264, 2,448,534 and 3,320,069.
  • the commonly used thioether ripening agents such as those disclosed in U.S. Patents 3,271,157, 3,574,628 and 3,737,313 can also be used.
  • thione compounds such as those disclosed in JP-A-53-82408 and JP-A-53-144319 can also be used.
  • the nature of the silver halide grains can be controlled by the presence of various compounds during the silver halide precipitation and formation process. Compounds of this type may be present in the reactor initially or they can be added along with the addition of one, two or more than two salts in accordance with the usual methods.
  • the characteristics of the silver halide can be controlled by the presence during the silver halide precipitation and formation process of compounds of copper, iridium, lead, bismuth, cadmium, zinc (chalcogen compounds of sulfur, selenium, tellurium for example), and compounds of gold and group VII precious metals, as disclosed in U.S.
  • the silver halide emulsions are generally sensitized chemically. Chemical sensitization can be achieved using active gelatin as disclosed on pages 67 - 76 of The Theory of the Photographic Process , by T.H. James, 4th edition, Macmillan, 1977, and by using sulfur, selenium, tellurium, gold, platinum, palladium, iridium or a combination of these sensitizing agents at pAg 5 - 10, pH 5 - 8 and at a temperature of from 30°C to 80°C, as disclosed in Research Disclosure , volume 120, April 1974, No. 12008, ibid volume 34, June 1975, No. 13452, U.S.
  • Chemical sensitization is carried out optimally in the presence of gold compounds and thiocyanate compounds, and in the presence of the sulfur containing compounds disclosed in U.S. Patents 3,857,711, 4,266,018 and 4,054,457 or sulfur containing compounds such as hypo, thiourea based compounds and rhodanine based compounds for example.
  • Chemical sensitization can be carried out in the presence of chemical sensitization promotors.
  • the compounds known as agents for inhibiting fogging in the chemical sensitization process and increasing photographic speed are used as chemical sensitization promotors.
  • chemical sensitization promotor improvers have been disclosed in U.S. Patents 2,131,038, 3,411,914 and 3,554,757, JP-A-58-126526 and the aforementioned book Photographic Emulsion Chemistry , by Duffin, pages 138 - 143.
  • Reduction sensitization can be achieved using hydrogen, for example, as disclosed in U.S.
  • Patents 3,891,446 and 3,984,249 or using stannous chloride, thiourea dioxide, polyamine or reducing agents of this type, and reduction sensitization by treatment at a low pAg value (for example less than 5) and/or a high pH value (for example greater than 8), as disclosed in U.S. Patents 2,518,698, 2,743,182 and 2,743,183 can be carried out in addition to, or in place of, chemical sensitization. Furthermore, color sensitivity can also be improved using the chemical sensitization methods disclosed in U.S. Patents 3,917,485 and 3,966,476.
  • the photosensitive materials used in the present invention may contain one or more types of surfactant as coating promotors, for anti-static purposes, for improving slip properties, for emulsification and dispersion purposes, for preventing the occurrence of sticking and for improving photographic characteristics (for example, for accelerating development, increasing contrast and increasing photographic speed) for example.
  • surfactant as coating promotors, for anti-static purposes, for improving slip properties, for emulsification and dispersion purposes, for preventing the occurrence of sticking and for improving photographic characteristics (for example, for accelerating development, increasing contrast and increasing photographic speed) for example.
  • the silver halide photographic emulsions used in the invention may be spectrally sensitized using cyanine dyes or by other means.
  • the dyes which can be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemi-cyanine dyes, styryl dyes and hemi-oxonol dyes.
  • Dyes classified as cyanine dyes, merocyanine dyes and complex merocyanine dyes are especially useful dyes. All of the nuclei normally used in cyanine dyes can be used for the basic heterocyclic nuclei in these dyes.
  • the nucleus may be a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus or a pyridine nucleus; a nucleus in which one of these nuclei is fused with an aliphatic hydrocarbon ring, or a nucleus in which one of these nuclei is fused with an aromatic hydrocarbyl ring, which is to say an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a be
  • the nucleus which has a ketomethylene structure in the merocyanine dyes or complex merocyanine dyes may be a five or six membered heterocyclic nucleus, for example a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thio-oxazolidin-2,4-dione nucleus, a thiazolidin-2,4-dione nucleus, a rhodanine nucleus or a thiobarbituric acid nucleus.
  • a pyrazolin-5-one nucleus for example a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thio-oxazolidin-2,4-dione nucleus, a thiazolidin-2,4-dione nucleus, a rhodanine nucleus or a thiobarbituric acid nucleus.
  • sensitizing dyes may be used individually or they may be used in combinations, and combinations of sensitizing dyes are often used in particular with the intention of achieving super-sensitization.
  • Substances which exhibit super-sensitization being dyes which themselves have no spectral sensitizing action or substances which essentially do not absorb visible light can be included in the emulsion together with the sensitizing dyes.
  • substituted aminostilbene compounds with a nitrogen containing heterocyclic group for example, those disclosed in U.S. Patents 2,933,390 and 3,635,721
  • aromatic organic acid/formaldehyde condensates for example, those disclosed in U.S.
  • Patent 3,743,510 and cadmium salts and azaindene compounds, for example, may be included.
  • the combinations disclosed in U.S. Patents 3,615,613, 3,615,641, 3,617,295 and 3,635,721 are especially useful.
  • Various compounds can be included in the material used in the present invention with a view, for example, to preventing the occurrence of fogging during the manufacture, storage or photographic processing of the photosensitive material, or with a view to stabilizing photographic performance.
  • anti-fogging agents or stabilizers such as azoles, for example benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mecaptotetrazoles (especially l-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; for example thioketo compounds such as oxazolinethione; azaindenes, for example
  • Gelatin is useful as a binding agent or protective colloid which can be used in the emulsion layers or intermediate layers of the photosensitive materials of the present invention, but other hydrophilic colloids can also be used.
  • gelatin derivatives graft polymers of other polymers with gelatin, proteins such as albumin and casein, cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfate esters, sodium alginate and sugar derivatives such as starch derivatives, and various synthetic hydrophilic polymeric materials, for example homopolymers or copolymers such as poly(vinyl alcohol), partially acetalated poly(vinyl alcohol), poly(N-vinylpyrrolidone), poly(acrylic acid), poly(methacrylic acid), polyacrylamide, polyvinylimidazole and polyvinylpyrazole, can be used.
  • gelatin hydrolyzates can also be used.
  • the photosensitive materials used in the present invention may contain inorganic or organic film hardening agents in any of the hydrophilic colloid layers which form the photographic photosensitive layer or the backing layer.
  • Chromium salts, aldehydes (for example, formaldehyde, glyoxal, glutaraldehyde), and N-methylol compounds (for example, dimethylolurea) can be cited as actual examples of such compounds.
  • active halogen compounds for example, 2,4-dichloro-6-hydroxy-1,3,5-triazine and its sodium salt
  • active vinyl compounds for example, 1,3-bis-vinylsulfonyl-2-propanol, 1,2-bis(vinylsulfonylacetamido)ethane or vinyl based polymers which have vinyl groups in side chains
  • hydrophilic colloids such as gelatin and providing stable photographic characteristics
  • N-Carbamoylpyridinium salts for example, (1-morpholinocarbonyl-3-pyridinio)methanesulfonate
  • haloamidinium salts for example, 1-(1-chloro-1-pyridinomethylene)pyrrolidinium 2-naphthalenesulfonate
  • the photographic emulsion layers and other layers in the photographic photosensitive materials used in the present invention can be coated onto a flexible support such as a plastic film, paper or cloth for example, or onto a rigid support such as glass, porcelain or metal for example, of the type normally used for photographic photosensitive materials.
  • Useful flexible supports include, for example, films made of semi-synthetic or synthetic polymers, such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, poly(vinyl chloride), poly(ethylene terephthalate) or polycarbonate for example, and papers which have been coated or laminated with a baryta layer or an ⁇ -olefin polymer (for example polyethylene, polypropylene, ethylene/butene copolymer).
  • the support may be colored using dyes or pigments. It may also be colored black for light shielding purposes.
  • the surface of the support is usually undercoated to improve adhesion with the photographic emulsion layer for example.
  • the surface of the support may be subjected to a glow discharge treatment, a corona discharge treatment, ultraviolet irradiation or a flame treatment, for example, before or after the undercoating treatment.
  • the present invention can be applied to various color photosensitive materials.
  • Typical applications include color negative films for general and cinematographic purposes, color reversal films for slides and television purposes, color papers, color positive films and color reversal papers, color diffusion transfer type photosensitive materials and heat developable type color photosensitive materials.
  • Color couplers are compounds which can form dyes by means of a coupling reaction with the oxidized form of a primary aromatic amine developing agent.
  • Typical examples of useful color couplers include naphthol or phenol based compounds, pyrazolone or pyrazoloazole based compounds, and open chain or heterocyclic ketomethylene compounds.
  • Examples of these cyan, magenta and yellow couplers which can be used in the invention include the compounds disclosed in the patents cited in Research Disclosure 17643 (December 1978), section VII-D, and ibid , No. 18717 (published 1979).
  • the color couplers which are incorporated in the photosensitive material are preferably rendered non-diffusible by having ballast groups or by polymerization.
  • Two-equivalent color couplers which are substituted with a coupling leaving group are preferable to the four-equivalent couplers which have a hydrogen atom at the coupling active site in that they enable the amount of coated silver to be reduced.
  • couplers of which the colored dye has a suitable degree of diffusibility, non-color forming couplers, or DIR couplers which release development inhibitors as the coupling reaction proceeds or couplers which release development accelerators as the coupling reaction proceeds can also be used.
  • the oil protected type acylacetamide based couplers are typical of the yellow couplers which can be used in the present invention. Examples have been disclosed, for example, in U.S. Patents 2,407,210, 2,875,057 and 3,265,506. The use of two-equivalent yellow couplers is preferred in the present invention. Typical examples include the oxygen atom elimination-type yellow couplers disclosed, for example, in U.S. Patents 3,408,194, 3,447,928, 3,933,501 and 4,022,620, and the nitrogen atom elimination-type yellow couplers disclosed, for example, in JP-B-58-10739, U.S.
  • Patents 4,401,752 and 4,326,024, RD 18053 (April 1979), British Patent 1,425,020, and West German Patent Application Laid Open Nos. 2,219,917, 2,261,361, 2,329,587 and 2,433,812.
  • ⁇ -pivaloylacetanilide based couplers provide colored dyes which have excellent fastness, especially light fastness, while ⁇ -benzoylacetanilide based couplers provide high color densities.
  • Oil protected type indazolone based or cyanoacetyl based, and preferably 5-pyrazolone based and pyrazoloazole, for example pyrazolotriazole, based couplers can be cited as magenta couplers which can be used in the present invention.
  • the 5-pyrazolone based couplers which have an arylamino group or an acylamino group substituted in the 3-position are preferred from the point of view of the hue of the colored dye and the color density. Typical examples have been disclosed, for example, in U.S. Patents 2,311,082, 2,343,703, 2,600,788, 2,908,573, 3,062,653, 3,152,896 and 3,936,015.
  • the nitrogen atom leaving groups disclosed in U.S. Patent 4,310,619 and the arylthio groups disclosed in U.S. Patent 4,351,897 are especially desirable as leaving groups for two-equivalent 5-pyrazolone based couplers. Furthermore, the 5-pyrazolone based couplers which have ballast groups disclosed in European Patent 73,636 provide high color densities.
  • the imidazo[1,2-b]pyrazoles disclosed in U.S. Patent 4,500,630 are preferred in view of the slight absorbance on the yellow side and the light fastness of the colored dye.
  • the pyrazolo[1,5-b][1,2,4]-triazoles disclosed in U.S. Patent 4,540,654 are especially desirable in this respect.
  • the oil protected-type naphthol based and phenol based couplers are cyan couplers which can be used in the present invention.
  • Typical examples include the naphthol based couplers disclosed in U.S. Patent 2,474,293, and the oxygen atom elimination-type two-equivalent naphthol based couplers disclosed in U.S. Patents 4,052,212, 4,146,396, 4,228,233 and 4,296,200 are preferred.
  • examples of phenol based couplers have been disclosed, for example, in U.S. Patents 2,369,929, 2,801,171, 2,772,162 and 2,895,826.
  • the use of cyan couplers which are fast to moisture and temperature are preferred in this invention.
  • Typical examples of such couplers include the phenol based cyan couplers which have an alkyl groups comprising an ethyl or larger group in the meta position of the phenol ring disclosed in U.S. Patent 3,772,002, the 2,5-diacylamino substituted phenol based couplers disclosed, for example, in U.S. Patents 2,772,162, 3,758,308, 4,126,396, 4,334,011 and 4,327,173, West German Patent Laid Open 3,329,729 and European Patent 121,365, and the phenol based couplers which have a phenylureido group in the 2-position and an acylamino group in the 5-position disclosed, for example, in U.S.
  • Patents 3,446,622, 4,333,999, 4,451,559 and 4,427,767 The cyan couplers which have a sulfonamido group or an amido group for example substituted in the 5-position of the naphthol ring disclosed in Japanese Patent Application Nos. 59-93605, 59-264277 and 59-268135 also provide color images which have superior fastness and their use is preferred in the present invention.
  • Graininess can be improved by the conjoint use of couplers for which the resulting colored dyes have a suitable degree of diffusibility.
  • blurring couplers of this type include the magenta couplers disclosed in U.S. Patent 4,366,237 and British Patent 2,125,570, and the yellow, magenta and cyan couplers disclosed in European Patent 96,570 and West German Patent Application Laid Open 3,234,533.
  • the dye forming couplers and the special couplers above mentioned can take the form of dimers or larger polymers.
  • Typical examples of polymerized dye forming couplers have been disclosed in U.S. Patents 3,451,820 and 4,080,211.
  • Examples of polymerized magenta couplers have been disclosed in British Patent 2,102,173, U.S. Patent 4,367,282, and Japanese Patent Application Nos. 60-75041 and 60-113596.
  • Two or more of the various types of coupler used in this present invention can be used conjointly in a layer of the same color sensitivity, and the same compound can be introduced into two or more different layers, in order to satisfy the characteristics required of the photosensitive material.
  • the couplers can be introduced into a photosensitive material using a variety of known methods of dispersion, for example using the solid dispersion method or the alkali dispersion method, preferably using the latex dispersion method, and most desirably using the oil in water dispersion method for example.
  • the oil in water dispersion method after dissolution in either a high boiling point organic solvent having a boiling point at least 175°C or a so-called auxiliary solvent having a low boiling point or in a mixture of such solvents, the solution is finely dispersed in water or an aqueous medium such as an aqueous gelatin solution for example in the presence of a surfactant.
  • high boiling point organic solvents have been disclosed, for example, in U.S. Patent 2,322,027.
  • the dispersion may be accompanied by a phase reversal and, where required, the auxiliary solvent may be reduced or removed by evaporation, noodle washing or ultrafiltration before the dispersion is used for coating.
  • high boiling point solvents examples include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate), phosphoric acid or phosphonic acid esters (for example, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl tri-2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, phosphate, tri-dodecyl phosphate, tri-butoxyethyl phosphate, tri-chloropropyl phosphate, di-2-ethylhexyl phenyl phosphonate), benzoic acid esters (for example, 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl p-hydroxybenzoate), amides (for example, N,N-diethy
  • organic solvents which have a boiling point above about 30°C, and preferably of at least 50°C, but below about 160°C, can be used as auxiliary solvents.
  • Typical examples of these solvents include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate and dimethylformamide.
  • a processing temperature is generally selected between 18°C and 50°C, but the processing temperature may be lower than 18°C or in excess of 50°C.
  • Color photographic processing comprised of a development process in which a dye image is formed can be used.
  • Known developing agents such as dihydroxybenzenes (for example, hydroquinone), 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone) and aminophenols (for example, N-methyl-p-aminophenol) can be used individually or in combination in a black and white developer.
  • dihydroxybenzenes for example, hydroquinone
  • 3-pyrazolidones for example, 1-phenyl-3-pyrazolidone
  • aminophenols for example, N-methyl-p-aminophenol
  • a color developer is comprised of an alkaline aqueous solution which contains a color developing agent.
  • the known primary aromatic amine developing agents such as the phenylenediamines (for example, 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline, 4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesulfonamidoethylaniline, 4-amino-3-methyl-N-ethyl-N- ⁇ -methoxyethylaniline) can be used as the color developing' agent.
  • the developers can also contain pH buffers such as alkali metal sulfites, carbonates, borates and phosphates, and development inhibitors or anti-foggants such as bromide, iodide and organic anti-foggants other than the compounds of this present invention.
  • pH buffers such as alkali metal sulfites, carbonates, borates and phosphates
  • development inhibitors or anti-foggants such as bromide, iodide and organic anti-foggants other than the compounds of this present invention.
  • They may also contain, as required, hard water softening agents, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethyleneglycol, development accelerators such as polyethyleneglycol, quaternary ammonium salts and amines, dye forming couplers, competitive couplers, fogging agents such as sodium borohydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, thickeners, the polycarboxylic acid based chelating agents disclosed in U.S. Patent 4,083,723 and the antioxidants disclosed in West German Patent Laid Open (OLS) 2,622,950 for example.
  • hard water softening agents preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethyleneglycol
  • development accelerators such as polyethyleneglycol, quaternary ammonium salts and amines
  • dye forming couplers such as quaternary ammonium salts and amines
  • dye forming couplers such
  • the color developed photographic photosensitive material is generally subjected to a bleaching process.
  • the bleaching proces may be carried out at the same time as the fixing process or it may be carried out separately.
  • Compounds of multi-valent metals such as iron(III), cobalt(III), chromium(VI) and copper(II), peracids, quinones, and nitroso compounds, for example, can be used as bleaching agents.
  • aminopolycarboxylic acids such as ethylenediamine tetra-acetic acid, nitrilotriacetic acid and 1,3-diamino-2-propanol tetra-acetic acid
  • organic acids such as citric acid, tartaric acid and malic acid
  • persulfate permanganate
  • nitrosophenol for example
  • potassium ferricyanide, ethylenediamine tetra-acetic acid iron(III) complex salts and 1,3-diaminopropane tetra-acetic acid iron(III) sodium salt and ethylene diamine tetra-acetic acid iron(III) ammonium salt are especially useful.
  • Ethylenediamine tetra-acetic acid iron(III) complex salts are useful in both independent bleach baths and single bath bleach-fix baths.
  • the bleaching accelerators disclosed, for example, in U.S. Patents 3,042,520 and 3,241,966, JP-B-45-8506 and JP-B-45-8836, the thiol compounds disclosed in JP-A-53-65732 and various other additives can also be added to the bleach and bleach-fix baths.
  • the water washing process is in some cases carried out in a single tank, but it is often carried out using a multi-stage counter-flow water washing system with two or more tanks.
  • the amount of water used in the washing process can be determined arbitrarily as required in accordance with the type of color photosensitive material, but it can also be calculated using the method described by S.R. Goldwasser in "Water Flow Rates in Immersion Washing of Motion Picture Film", published on pages 248 - 253 of Journal of Motion Picture and Television Engineering, volume 64 (May 1955) for example.
  • the amount of water used is generally from 100 ml to 2000 ml per square meter of color photosensitive material, but the use of from 200 ml to 1000 ml is preferred from the viewpoints of both the stability of the colored image and the water economy.
  • the pH value in the washing process is generally within the range from 5 to 9.
  • photosensitive materials used in this present invention When photosensitive materials used in this present invention are applied in the color diffusion photographic method, they can have a film unit construction of the peel apart type or of the unified (integrated) type as disclosed in JP-B-46-16356, JP-B-48-33697, JP-A-50-13040 and U.S. Patent 1,330,524, or of the type where peeling apart is unnecessary as disclosed in JP-A-57-119345.
  • a polymeric acid layer which is protected by a neutralizing timing layer is useful for widening the permissible processing temperature latitude.
  • these may be added to any layer in the sensitive material, or they may be sealed into the processing liquid container as a developer component.
  • combinations of at least three silver halide emulsion layers which are photosensitive to different spectral regions are used in order to obtain a wide range of colors in the chromaticity diagram using the three primary colors yellow, magenta and cyan.
  • combinations of blue, green and red sensitive layers, and combinations of green, red and infrared sensitive layer can be used.
  • The' photosensitive layers can be arranged in the various orders known for color photographic materials. Furthermore, each of these photosensitive layers may be divided into two or more layers as required.
  • Solutions (I) and (II) indicated below were added simultaneously at an even flow rate over a period of 30 minutes to a thoroughly agitated aqueous gelatin solution (a solution obtained by adding 20 grams of gelatin, 0.3 gram of potassium bromide, 6 grams of sodium chloride and 30 mg of reagent A indicated below to 800 ml of water and maintaining at a temperature of 50°C). Subsequently, solutions (III) and (IV) indicated below (Table 1) were added simultaneously over a period of 30 minutes. Furthermore, the dye solution of Table 2 was added over a period of 20 minutes starting 3 minutes after the commencement of the addition of solutions (III) and (IV).
  • Solution (I) and solution (II) shown in Table 4 were added over a period of 30 minutes to a thoroughly agitated aqueous gelatin solution (Table 3) which was being maintained at 50°C. Next, solution (III) and solution (IV) shown in Table 4 were added aver a period of 30 minutes and the dye solution shown in Table 5 was added 1 minute after completion of this addition.
  • the emulsion obtained was a mono-disperse cubic emulsion of average grain size 0.40 ⁇ and the recovery was 630 grams.
  • Solution (I) and solution (II) indicated below were added simultaneously over a period of 30 minutes to a thoroughly agitated aqueous gelatin solution (obtained by adding 20 grams of gelatin, 3 grams of potassium bromide, 0.03 gram of reagent A and 0.25 gram of HO(CH 2 ) 2 S(CH 2 ) 2 S(CH 2 ) 2 OH to 800 cc of water and maintaining at 50°C).
  • solution (III) and solution (IV) indicated below (Table 6-1) were added simultaneously over a period of 20 minutes.
  • the dye solution of Table 6-2 was added over a period of 18 minutes starting 5 minutes after the commencement of the addition of solution (III).
  • Zinc hydroxide of an average particle size of 0.2 ⁇ m (12.5 grams), 0.1 gram of poly(sodium acrylate) and 1 gram of carboxymethylcellulose as a dispersant were added to 100 ml of 4% aqueous gelatin solution and pulverized for 30 minutes using glass beads of an average diameter 0.75 mm in a mill. The glass beads were then removed and a dispersion of zinc hydroxide was obtained.
  • Active carbon powder (special reagent grade, 2.5 grams) made by the Wako Pure Drug Co. and 0.25 gram of polyethylene glycol nonylphenyl ether and 1 gram of Temol N made by the Kao Soap Co. as a dispersant were added to 100 ml of 5% aqueous gelatin solution and pulverized for 120 minutes using glass beads of average diameter 0.75 mm in a mill. The glass beads were then removed and a dispersion of active carbon of an average particle size 0.5 ⁇ was obtained.
  • the electron transfer agent (10) indicated below (10 grams), 0.5 gram of the anionic surfactant indicated below and 0.5 gram of polyethyleneglycol nonylphenyl ether as dispersant were added to a 5% aqueous gelatin solution and pulverized for 60 minutes using glass beads of an average diameter 0.75 mm in a mill. The glass beads were then removed, and a dispersion of an electron transfer agent of average particle size 0.3 ⁇ was obtained.
  • the yellow magenta and cyan formulations are shown in Table 7, and these were added to 50 ml of ethyl acetate in each case and heated to about 60°C and dissolved to provide uniform solutions. The solution was then mixed with agitation with 100 ml of 10% aqueous lime treated gelatin solution, 0.6 gram of sodium dodecylbenzenesulfonate and 50 ml of water, and then dispersed at 10000 rpm for 10 minutes in a homogenizer. The dispersion obtained was referred to as a gelatin dispersion of the dye donating compound.
  • the electron donor (4) indicated below (23.6 grams) and 8.5 grams of the above mentioned high boiling point solvent (2) were added to 30 ml of ethyl acetate, and a uniform solution was obtained.
  • the multi-layer color photosensitive element (1) for diffusion transfer purposes of which the structure is shown in Table 8 was prepared using these dispersions etc.
  • Photosensitive element (2) was then prepared in exactly the same way as photosensitive element (1) except that 200 mg/m 2 of ⁇ -carrageenan was added to each of the second, fourth and sixth layers.
  • a dye fixing element (1) which had the first to third coated layers coated on the support (1) which had been pre-coated with the first and second backing layers was prepared as shown in Table 9.
  • the first to third layers were coated simultaneously with coated layer thicknesses of 15 cc/m 2 , 40 cc/m 2 and 15 cc/m 2 respectively.
  • the dye fixing element (2) was prepared in the same way as dye fixing element (1) except that the gelatin in the third layer was replaced by the same amount of agar
  • Dye fixing element (3) was prepared in the same way as dye fixing element (1) except that the gelatin in the third layer was replaced by the same amount of ⁇ -carrageenan
  • Dye fixing element (4) was prepared in the same way as dye fixing element (1) except that the gelatin in the third layer was replaced by the same amount of ⁇ -carrageenan
  • Dye fixing element (5) was prepared in the same way as dye fixing element (1) except that the gelatin in the third layer was replaced by 0.05 g/m 2 of phaeceleran.
  • the dye fixing elements (1) to (6) which had been prepared were cut into 10 cm squares and left to stand with the third layer side uppermost on a flat surface, and the amount of curl (the average lift of the four corners) was measured after standing for 12 hours at 25°C, 20% RH.
  • Photosensitive element (1) was exposed using a tungsten lamp at 5000 lux for 1/10th second through B, G, R and gray color separation filters of which the density changed continuously.
  • the exposed photosensitive element was then fed at a line speed of 22 mm/sec, water was supplied at a rate of 15 ml/m 2 to the emulsion surface using a wire bar, and then this element was laminated immediately in contact with the film surface of each of the dye fixing elements (1) to (6).
  • the laminates were then heated for 15 seconds using a heated roller the temperature of which was controlled in such a way that the temperature of the film which had taken up the water was set at 85°C.
  • the dye fixing elements On peeling away the dye fixing elements subsequently clear blue, green, red and gray images corresponding to the B, G, R and gray color separation filters were obtained without unevenness on the dye fixing elements.
  • the coated surfaces of the parts of the image of maximum density (D max ) and minimum density (D min) obtained were placed together face to face and subjected to a load of 2 kg/m 2 , and after leaving to stand for 12 hours under conditions of 30°C, 70% RH, the density of the minimum density part was measured.
  • Photosensitive elements (1) and (2) were exposed at 5000 lux for 1/10th second using a tungsten lamp through B, G, R and Gray color separation filters of a density which changed continuously.
  • the exposed photosensitive elements were fed at a line speed of 20 mm/sec, water was supplied to the emulsion surface at a rate of 15 ml/m 2 using a wire bar. Immediately afterwards they were laminated in such a way that the film surface was in contact with a dye fixing element (3).
  • the laminates were then heated for 15 seconds using a heated roller the temperature of which was controlled in such a way that the temperature of the film which had taken up the water was set to 85°C.
  • a heated roller the temperature of which was controlled in such a way that the temperature of the film which had taken up the water was set to 85°C.
  • test samples for which photosensitive elements (1) and (2) had been used immediately after coating were taken as samples A and the test samples obtained using the photosensitive elements (1) and (2) after storage at 40°C, 75% RH were taken as samples B.
  • the dye fixing element (7) was prepared by providing a coated layer structure of the first to the third layers on a support (1) (the same as described in Example 1) which had been prepared by the pre-coating of the first and second backing layers on a support comprised of top quality paper which had been laminated with polyethylene.
  • coating was carried out simultaneously in such a way that the coating liquid film thickness for the first to the third layers was 15 cc/m 2 , 40 cc/m 2 and 15 cc/m 2 respectively.
  • Solution (I) and solution (II) of Table 15 were added over a period of 30 minutes to a thoroughly agitated aqueous gelatin solution (Table 14) which was being maintained at 50°C. Next, solution (III) and solution (IV) of Table 15 were added with the addition times shown in Table 17. The dye solution shown in Table 16 was also added as indicated in Table 17.
  • Emulsions (1) to (3) shown in Table 17 were prepared in this way, and all of the emulsions obtained were cubic emulsions of average grain size 0.40 ⁇ and the recovery in each case was 630 grams.
  • the two-layer structure indicated below was coated onto a 100 ⁇ PET support.
  • the photosensitive element was exposed at 5000 lux for 1/10th second using a tungsten lamp through a gray filter of which the density changed continuously.
  • the exposed photosensitive elements were fed at a line speed of 20 mm/sec, water was supplied to the emulsion surface at a rate of 15 ml/m 2 using a wire bar and immediately afterwards they were laminated in such a way that the film surface was in contact with the dye fixing elements (7), respectively.
  • the laminates were then heated for 15 seconds using a heated roller of which the temperature was controlled in such a way that the temperature of the film which had taken up the water was set to 85°C. On subsequently peeling away the dye fixing element, clear magenta images without unevenness were obtained on the dye fixing elements.
  • a photosensitive element was prepared as shown in Table 20.
  • the photosensitive element of the present invention is an excellent photosensitive element which has a high maximum density.
  • photosensitive material 401 The preparation of photosensitive material 401 is described below.
  • Solution (I) and solution (II) indicated below were added simultaneously at an even flow rate over a period of 30 minutes to a thoroughly agitated aqueous gelatin solution (obtained by adding 20 grams of gelatin, 0.3 gram of potassium bromide, 6 grams of sodium chloride and 30 mg of reagent A indicated below to 800 ml of water and maintaining at 50°C). Subsequently, solution (III) and solution (IV) indicated below were added simultaneously over a period of 30 minutes. Furthermore, a solution of a mixture of the dyes indicated below was added starting 3 minutes after the commencement of the addition of solutions (III) and (IV).
  • Solution (I) and solution (II) indicated below were added simultaneously over a period of 30 minutes to a thoroughly agitated aqueous gelatin solution (obtained by adding 20 grams of gelatin, 0.30 gram of potassium bromide, 6 grams of sodium chloride and 0.015 gram of reagent A to 730 ml of water and maintaining at 60°C).
  • a thoroughly agitated aqueous gelatin solution obtained by adding 20 grams of gelatin, 0.30 gram of potassium bromide, 6 grams of sodium chloride and 0.015 gram of reagent A to 730 ml of water and maintaining at 60°C.
  • solution (III) and solution (IV) indicated below were added over a period of 30 minutes, and a solution of the dye indicated below was added 1 minute after completion of this addition.
  • the emulsion obtained was a mono-disperse cubic emulsion of an average grain size 0.40 ⁇ m, and the recovery was 630 grams.
  • Solution (I) and solution (II) indicated below were added simultaneously over a period of 30 minutes to a thoroughly agitated aqueous gelatin solution (obtained by adding 20 grams of gelatin, 3 grams of potassium bromide, 0.03 gram of reagent A indicated below and 0.25 gram of HO(CH 2 ) 2 S(CH 2 ) 2 S(CH 2 ) 2 OH to 800 ml of water and maintaining at 50°C). Subsequently, solution (III) and solution (IV) indicated below were added simultaneously over a period of 20 minutes. Furthermore, a solution of the two dyes indicated below was added 5 minutes after the commencement of the addition of solution (III).
  • the electron donor (4) indicated below (23.6 grams) and 8.5 grams of the above mentioned high boiling point solvent (2) were added to 30 ml of ethyl acetate and heated to 60°C, and a uniform solution was obtained.
  • the image receiving material 401 which had coated layers of the structure of the first to the third coated layers coated on the support (1) (the same as described in Example 1) which had been pre-coated with the first and second backing layers was prepared as shown in Table 23 below. No hydrophilic organic solvent was used in the dissolution or dispersion in water of the components shown in the Table when preparing the coating liquid for the third layer.
  • the first to third layers were coated simultaneously with a multi-layer coating system with coated layer thicknesses of 15 ml/m 2 , 40 ml/m 2 and 15 ml/m 2 respectively for the first to the third layers.
  • Image receiving material 402 was prepared by a different method for the addition of the ⁇ -carrageenan. First of all, the ⁇ -carrageenan was dispersed in five times it weight of methanol. Next, water was added to the dispersion and a 3 wt ⁇ % aqueous ⁇ -carrageenan solution was prepared. In this case, the ⁇ -carrageenan dissolved rapidly in the water and no lumps were formed. This solution of ⁇ -carrageenan was added to the coating liquid for the third layer and coated in the same way as for image receiving material 401.
  • the photosensitive material 401 was exposed at 5000 lux for 1/10th second to tungsten light through a gray wedge of which the density changed continuously.
  • the exposed photosensitive materials were fed at a line speed of 20 mm/sec, water was supplied to the emulsion surface at a rate of 15 ml/m 2 using a wire bar. Immediately afterwards they were laminated in such a way that the film surfaces were in contact with an image receiving material. The laminates were then heated for 15 seconds using a heated roller of which the temperature was controlled in such a way that the temperature of the film which had taken up the water was set to 85°C, and on subsequently peeling away the image receiving material, clear gray images were obtained on the image receiving materials.

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Claims (12)

  1. Photographisches Material für das Diffusionsübertragungsverfahren, umfassend einen Träger mit mindestens einem darauf aufgebrachten lichtempfindlichen Element, umfassend eine lichtempfindliche Silberhalogenidemulsion und eine Verbindung, die einen diffusionsfähigen Farbstoff liefert, und ein Farbstoff fixierendes Element, das auf dem lichtempfindlichen Element zum Zeitpunkt der Bildübertragung aufgebracht ist, wobei das Farbstoff fixierende Element ein natürliches makromolekulares Polysaccharid enthält, das aus Rotalgen stammt.
  2. Photographisches Material für das Diffusionsübertragungsverfahren nach Anspruch 1, worin das natürliche makromolekulare Polysaccharid, das aus Rotalgen stammt, ein natürliches makromolekulares Polysaccharid ist, ausgewählt aus Agar, κ-Carrageenan, λ-Carrageenan,
    Figure imgb0062
    -Carrageenan und Phaeceleran.
  3. Photographisches Material für das Diffusionsübertragungsverfahren nach Anspruch 1, worin das lichtempfindliche Element weiterhin ein Bindemittel, ein Elektronenübertragungsmittel, einen Elektronendonator und eine reduzierbare, einen Farbstoff liefernde Verbindung, die bei der Reduktion einen diffusionsfähigen Farbstoff freisetzt, umfaßt.
  4. Photographisches Material für das Diffusionsübertragungsverfahren nach Anspruch 1, worin mindestens eine lichtempfindliche Silberhalogenidemulsion eine Gold/Schwefelsensibilisierte monodisperse Emulsion ist.
  5. Photographisches Material für das Diffusionsübertragungsverfahren nach Anspruch 1, worin mindestens eine lichtempfindliche Silberhalogenidemulsion einen sensibilisierenden Farbstoff umfaßt, der vor der chemischen Sensibilisierung adsorbiert wurde.
  6. Verfahren zur Herstellung eines photographischen Materials für das Diffusionsübertragungsverfahren, umfassend einen Träger mit mindestens einem darauf aufgebrachten lichtempfindlichen Element, umfassend eine lichtempfindliche Silberhalogenidemulsion und eine Verbindung, die einen diffusionsfähigen Farbstoff liefert, und ein Farbstoff fixierendes Element, das auf dem lichtempfindlichen Element zum Zeitpunkt der Bildübertragung aufgebracht ist, wobei das Verfahren das Einbringen eines natürlichen makromolekularen Polysaccharids, das aus Rotalgen stammt, in das Farbstoff fixierende Element umfaßt.
  7. Verfahren nach Anspruch 6, worin das natürliche makromolekulare Polysaccharid, das aus Rotalgen stammt, ein natürliches makromolekulares Polysaccharid ist, ausgewählt aus Agar, κ-Carrageenan, λ-Carrageenan,
    Figure imgb0062
    -Carrageenan und Phaeceleran.
  8. Verfahren nach Anspruch 6, weiterhin umfassend die Verwendung einer Beschichtungsflüssigkeit, enthaltend eine Lösung eines wasserlöslichen Polymers, umfassend ein natürliches makromolekulares Polysaccharid, ein hydrophiles organisches Lösungsmittel, in dem das wasserlösliche Polymer im wesentlichen unlöslich ist, und Wasser.
  9. Verfahren nach Anspruch 6, worin das Einbringen des natürlichen makromolekularen Polysaccharids in das Farbstoff fixierende Element das Aufbringen einer Beschichtungsflüssigkeit, umfassend das natürliche makromolekulare Polysaccharid, ein hydrophobes organisches Lösungsmittel, in dem das Polysaccharid im wesentlichen unlöslich ist, und Wasser, auf dem Farbstoff fixierenden Element umfaßt.
  10. Verfahren nach Anspruch 6, worin das lichtempfindliche Element weiterhin ein Bindemittel, ein Elektronenübertragungsmittel, einen Elektronendonator und eine reduzierbare, einen Farbstoff liefernde Verbindung, die bei der Reduktion einen diffusionsfähigen Farbstoff freisetzt, umfaßt.
  11. Verfahren nach Anspruch 6, worin mindestens eine lichtempfindliche Silberhalogenidemulsion eine Gold/Schwefelsensibilisierte monodisperse Emulsion ist.
  12. Verfahren nach Anspruch 6, worin mindestens eine lichtempfindliche Silberhalogenidemulsion einen sensibilisierenden Farbstoff umfaßt, der vor der chemischen Sensibilisierung adsorbiert wurde.
EP91102365A 1990-02-20 1991-02-19 Polysaccharide enthaltende photographische Materialien Expired - Lifetime EP0443529B1 (de)

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JP3929690A JP2649853B2 (ja) 1990-02-20 1990-02-20 拡散転写写真材料
JP10010190A JPH03296736A (ja) 1990-04-16 1990-04-16 水溶性ポリマーの塗布方法
JP100101/90 1990-04-16
JP10310590A JPH043055A (ja) 1990-04-20 1990-04-20 熱現像感光材料
JP103105/90 1990-04-20

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US6482503B1 (en) * 1993-03-19 2002-11-19 Xerox Corporation Recording sheets containing pyrrole, pyrrolidine, pyridine, piperidine, homopiperidine, quinoline, isoquinoline, quinuclidine, indole, and indazole compounds
US5970271A (en) * 1997-03-11 1999-10-19 Polaroid Corporation Spool caddy for use with dry optical image processing of roll film
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JP3802288B2 (ja) * 1999-04-16 2006-07-26 味の素株式会社 油性原料組成物
US6573036B2 (en) * 2000-04-10 2003-06-03 Afga-Gevaert Single-side coated silver halide photographic film material having reduced tendency to curl
US6485896B2 (en) * 2000-12-06 2002-11-26 Eastman Kodak Company Emulsion composition to control film core-set
EP1491952B1 (de) * 2003-06-23 2015-10-07 Sumitomo Bakelite Co., Ltd. Positiv arbeitende lichtempfindliche Harzzusammensetzung, Verfahren zur Herstellung eines strukturierten Harzfilms, Halbleitervorrichtung, Anzeigevorrichtung, und Verfahren zur Herstellung der letzteren
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